O-methyl/ethyl-S-propyl/butyl-O-chloroallylphenyl thiophosphates and dithiophosphates

ABSTRACT

Thiophosphoric and dithiophosphoric acid esters of the formula   WHEREIN R1 represents methyl or ethyl, R2 represents n-propyl, isobutyl or sec, butyl, R3 and R4 each represents chlorine, bromine, methyl or ethyl, R5 represents   X represents oxygen or sulphur, processes for their manufacture and their use in pest control.

United States Patent 191 Beriger et al.

[451 Aug. 5, 1975 I O-METHYL/ETHYL-S-PROPYL/BUTYL-O- CHLOROALLYLPHENYL THIOPHOSPHATES AND DITHIOPHOSPHATES [75] Inventors: Ernst Beriger, Allschwil.

Switzerland; Manfred Boger, I-Ialtingen, Germany; Jozef Drabek, Allschwil; Odd Kristiansen, Reinach, both of Switzerland [73] Assignee: Ciba-Geigy Corporation, Ardsley,

[22] Filed: Oct. 23, 1973 [21] Appl. No.: 408,874

[30] Foreign Application Priority Data Nov. 3. 1972 Switzerland... 16043/72 Sept. 21, 1973 Switzerland 13638/73 [52] US. Cl 260/956; 260/327 M; 260/340.7; 260/340.9; 260/454; 260/923; 260/944;

Primary E.\'aminerAnton H. Sutto Assistant E.\'uminerRichard L. Raymond Attorney, Agent, or Firm-Frederick H. Rabin [5 7] ABSTRACT Thiophosphoric and dithiophosphoric acid esters of the formula wherein R represents methyl or ethyl, R represents n-propyl, isobutyl or sec, butyl,

R and R each represents chlorine, bromine,

methyl or ethyl. R,-, represents o- CH3 0 3 cu -CH 3 011 0C'-C-alkyl 1 4 v .0 s 411/] -cn \S v \S I c -C -alt yl a d X represents oxygen or sulphur, processes for their manufacture and their use in pest control.

10 Claims, No Drawings 1 O-METHYL/ETHYL-S-PROPYL/BUTYL-O- CHLOROALLYLPHENYL THIOPHOSPHATES AND DITHIOPHOSPHATES The present invention relates to thiophosphoric' and 5 dithiophosphoric acid esters, process for their manufacture, and to their use in pest control.

The thiophosphoric and dithiophosphoric acid esters have the formula 0- -CH2CH=CHC1, -CHO, -cu J 0 CH ..CH/ -CH/] a 40 3 '0 cu "CH 3 a 'H 45 OLCH3 00 -c -a1ky1 1 m oc -c y CH3 2 sc -c alkyl S\CH C -C -alkyl and X represents oxygen or sulphur.

The alkenyloxy, alkinyloxy, alkoxyalkyleneoxy, or

alkenylthio groups possible for R can be straight-chain or branched. Examples of such groups include: allyloxy, methallyloxy, proparglyloxy, l-methyl-2- propinyloxy, l, l -dimethyl-2-propinyloxy, l -methyl-2- methoxy)-ethoxy, Z-mcthoxy-ethoxy,2-methoxyethoxy, 2-ethoxy-ethoxy, allylthio, methallylthio.

The alkyl moieties of an acetal, thioacetal, nalkylformimino, N-alkylhydrazono or N,N-

.dialkylhydrazono group R are straight-chain. Examples of such alkyl moieties include: methyl, ethyl.

A preferred group of compounds is that of the formula I, wherein R represents methyl or ethyl, R represents n-propyl or sec. butyl, R and R each represents hydrogen, chlorine, bromine, methyl or ethyl, R represents allyloxy, methallyloxy, 2-chloroallyloxy, 3- chloroallyloxy, propargyloxy, allylthio or methallylthio, and'X represents oxygen.

A further preferred group of compounds of the formula l is that wherein R, represents methyl or ethyl, R represents n-propyl or sec. butyl, R and R each represents hydrogen, chlorine, bromine, methyl or ethyl, R represents CHO, CH=N-@ CH=NC H (i),

OCH S-CH ..CH=NN(CH3)2 -CH 3 -cH 3 0on s-cH,

sc H SCH o CH\ 2 5 -CH/ 3 'CH\ sc n sc n o S and I 4 CH X represents oxygen.

Yet a further preferred group of compoundsv of the formula 1 is that wherein R represents-methyl or ethyl,

R represents n-propyl or sec. butyl, R and R each represents hydrogen, chlorine, bromine, methyl or ethyl, R represents 2-chloroallyl or 3-chloroallyl, and X represents oxygen.

Particularly to be highlighted on account of their action are the compounds of the formula I wherein R represents ethyl, R represents .n-propyl or see. butyl, R and R each represents hydrogen, chlorine, bromine or methyl, and R is in ortho-position and represents 2-chloroallyl or 3-chloroallyl, and X represents oxygen.

The compounds of the formula I can be manufactured by methods which are known per se, e.g. in the following manner:

R ll" 3 1 PS1 H La) R23 R4 (II) (111:)R

X R u R 1b) 1 P01 NED-Q5 R28 4 (1 R5 In the formulae II, III and IV, R to R and X have the meanings given for the formula I and Me represents an alkali metal, in particular sodium or potassium, ammonium or alkylammonium.

Process 1a and lb can be carried out at normal pressure, at a temperature of 080C, preferably 50C,

and in solvents and diluents that are inert towards the reactants.

Examples of suitable solvents or diluents are: ether and ethereal compounds, such as diethyl ether, dipropyl ether, dioxan, tetrahydrofuran; amides, such as N,N-dialkylated carboxy amides; aliphatic, aromatic,

and halogenated hydrocarbons, in particular, benzene, toluene, xylene, =chloroform, chlorobenzene; nitriles, such as acetonitrile.

The starting materials of the formula II are known and can be manufactured by a method analogous to e.g. that. described in -J. Org. Chem. 30 3217 (1965).

The active substances of the formula I are suitable for combating animal and plant pests of the most diverse kinds. In particular, they act effectivelyv against all development states, such as eggs, larvae, nymphs, pupae, and adults of"insjects;e.g. of the families:

Acrididae, 'Blat tidae; Gryllidae, Gryllotalpidae, Tettigoniidae, Cimicidae, Phyrrhocoridae, .Reduviidae, Aphididae, Delphacidae, Diaspididae, Pseudococcidae, Chrysomelidae, Coccinellidae, Bruchidae, Scarabaeidae, Dermestidae, Tenebrionidae, Curculionidae, Tineidae, Noctuidae, Lymantriidae, Pyralidae', Galleriidae, Culcidae, Tipulidae, Stomoxydae, Muscidae, Calliphoridae, Trypetidae, Pulicidae.

The compounds of the formula I are also active against eggs, larvae, and adults of representatives of the order Acarina, such as mites, spider mites, and ticks,

e.g. of the families: lxodidae, Argasidae, Tetranychidae, and Demanyssidae.

The insecticidal or acaricidal action can be substantially broadened and adapted to given circumstances by addition of other insecticides and/or acari'cides. Examples of suitable additives are: organic phosphorus compounds, derivatives of nitrophenols, formamidines, ureas, carbamates, and chlorinated hydrocarbons.

In addition to the above cited properties, the compounds of the formula I are also active against fungi, for exampel against the phytopathogenic fungi of the classes: Oomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Denteromycetes. They are also active against phytopathogenic nematodes.

The compounds of the formula I may be used as pure active substance or together with suitable carriers and- /or additives. Suitable carriers and additives can be solid or liquid and correspond to the substances conventionally used in formulation technology, for example natural or regenerated substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders and/or fertilisers.

Mag

For application, the compounds of the formula I may be processed to dusts, emulsion concentrates, granules, dispersions, sprays, to solutions, or suspensions, in the conventional formulation which is commonly employed in application technology.

' The agents according to the invention are manufactured in known manner by intimately mixing and/or grinding active substances of the formula I with the suitable carriers, optionally with the addition of dispersants or solvents which are inert towards the-active substances.

The active substances may take, and be used in, the following forms:

Solid forms:

Dusts, tracking agents, granules, coated granules, impregnated granules and homogeneous granules. Liquid forms:

a. active substances which are dispersible in water:

a) 5 partes of active substance 95 parts of talcum b) 2 pans of active substance 1 part of highly disperse silicic acid 97 parts of talcum.

The active substances are mixed with the carriers and ground.

Granules The following substances are used to produce 5% granules:

5 parts of active substance, 0.25 parts of epichlorohydrin, 0.25 parts of cetyl polyglycol ether, 3.50 parts of polyethylene glycol, 91 parts of kaolin (particle size 0.3 0.8 mm).

The active substance is mixed with epichlorohydrin and dissolved with 6 parts of acetone; the polyethylene glycol and cetyl polyglycol ether are then added. The thus obtained solution is sprayed on kaolin, and the acetone subsequently evaporated in vacuo.

Wettable Powder The following constituents are used for the preparation of a) a 40%, b) and c) a 25%, and d) a wettable powder:

a) 40 parts of active substance,

5 parts of sodium lignin sulphonate, l part of sodium dibutyl-naphthalene sulphonate, 54 parts of silicic acid. b) 25 parts of active substance,

4.5 parts of calcium lignin sulphonate, 1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture 1:1 1.5 parts of sodium dibutyl naphthalene sulphonate, 19.5 parts of silicic acid, 19.5 parts of Champagne chalk. 28.1 parts of kaolin. c) 25 parts of active substance,

2.5 parts of isooctylphenoxy-polyoxyethyleneethanol, 1.7 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1 8.3 parts of sodium aluminium silicate, 16.5 parts of kieselgur, 46 pans of kaolin. d) 10 parts of active substance,

3 parts of a mixture of the sodium salts of saturated fatty alcohol sulphates, 5 parts of naphthalenesulphonic acid/formaldehyde condensate, 82 parts of kaolin.

6 The active substances are intimately mixed, in suitable mixers, with the additives, the mixture being then ground in the appropriate mills and rollers. Wettable powders are obtained which can be diluted with water 5 to give suspensions of any desired concentration.

Emulsifiable Concentrates The following substances are used to produce a) a 10% and b) a 25% emulsifiable concentrate:

a) 10 parts of active substance,

3.4 parts of epoxidised vegetable oil,

13.4 parts of a combination emulsifier consisting of fatty alcohol polyglycol ether and alkylaryl sulphonate calcium salt,

40 parts of dimethylformamide,

43.2 parts of xylene,

parts of active substance,

2.5 parts of epoxidised vegetable oil,

10 parts of an alkylarylsulphonate/fatty alcoholglycol ether mixture,

5 parts of dimethylformamide,

57.5 parts of xylene.

From these concentrates it is possible to produce, by dilution with water, emulsions of any desired concentration.

Spray The following constituents are used to prepared a 5% spray:

5 parts of active substance, 1 part of epichlorohydrin, 94 parts of benzene (boiling limits l60Cl90C).

5 EXAMPLE 1 3 Manufacture of O-ethyl-S-(n)-propyl-O-4-formylphenyl-thiophosphoric acid ester 13.3 g of triethylamine are added to a solution of 17 g of 4-hydroxybenzaldehyde in 150 ml of benzene. 26.4 g of O-ethyl-S-(n)-propyl-chlorothiolphosphoric acid ester are added dropwise with constant stirring at l0-l5C. The reaction mixture is stirred for 12 hours at room temperature, then it is washed with water, 3% Na CO solution, and again with water, and dried over anhydrous sodium sulphate. The benzene is distilled off. Molecular distillation of the residue yields the compound of the formula Continued Physical Data 0 O O U! .11

g I [:Efn E $6] g Q J m CH CH c11 0 0 5 /SCH \SCH Continued R i 7 Physical Data CH:NN(CH 2 5 5 .5565 T Y U C;i 1\ Moi 22 @scl-i ,54 9

Y 11 1,5568 @scn CH (i:CH

B T r n5 1,5681 CH -fifCH In addition, the following compounds are manufactured in analogous manner:

S C H II 2 5 P-OR' n)C H S Physical Data' SCH @CH 3 n 1,5862 SCH Continued r Physi cal Dat ia l 26 O/CIKO :55 L

COCH L The following compounds are also manufactured in analogous manner:

Continued Compound Physical lJata 0 se C H S II o i c H s u 4 9 c H O P- 1,5284

CH CH=CH-Cl 0 sec. C H S ll cH cH=cH-c1 o i c H s u CH Li=CH 0 sec. C H- S ll CH -(i=CH O /SCH i c H s u 5 4 9O POCH 15625 2 5 \SCH O /SCH sec. C H S ll 3 4 9O n 1,5605 2 5 sc EXAMPLE 2 A. Insecticidal lngest Poison Action Tobacco plants were sprayed with a 0.05% aqueous emulsion (obtained from a 10% emulsifiable concentrate). After the coating had dried, the tobacco plants were populated with Spodoptera littoralis larvae L and with Heliothis virescens larvae L The testwas carried out at 24C and 60% relative humidity. In the above test, the compounds according to Example 1 exhibited good ingest poison action against Spodoptera littoralis and Heliothis virescens.

B. lnsecticidal Contact Action Broad beans (Vicia faba) reared in pots were infected with about 200 leaflice (Aphis fabae) per plant one day before the application. A spray broth in a concentration of 1,000 ppm (prepared from a 25% wettable powder) was applied to the leaves populated with lice using a compressed air spray. Evaluation took place 24 hours after the application. In the above test, the compounds according to Example 1 exhibited good contact action against Aphis fabae.

plied in granule form to the paddy water (rats of applia cation: 8 kg of active substance per hectare). Evaluation of the insecticidal action took place 10 days after application of the granules.

The compounds according to Example l were active in the above test against Chilo suppressalis.

EXAMPLE 4 Action Against Ticks A. Rhipicephalus bursa Five adult ticks and 50 tick larvae were counted into a glass tube and immersed for l to 2 minutes in 2 ml of an aqueous emulsion from an emulsion series each containing 100, 10, l and 0.1 ppm of test substance. The tube was then sealed with a standardised cotton wool plug and placed on its head, so that the active sub stance emulsion could be absorbed by the cotton wool.

In the case of the adults evaluation took place after 2 weeks, and in that of the larvae after 2 days. Each test was repeated twice.

B. Boophilus Microplus (Larvae) Tests were carried out in each case with OP- sensitive larvae using a dilution series analogous to that of test A. (The resistance refers to the tolerability of Diazinon).

The compounds according to Example I acted well in these tests against adults and larvae of Thipicephalus bursa and larvae of Boophilus microplus.

EXAMPLE 5 Action Against Spider Mites Phaseolus vulgaris (dwarf beans) had an infested piece of leaf from a mass culture of Tetranychus urticae placed on them 12 hours before the test for the acaricidal action. The mobile stages which had migrated were sprayed with the emulsified test preparations from a chromotography atomiser so that the spray broth did not run off. The number of living and dead larvae, adults and eggs were evaluated after 2 to 7 days under a stereoscopic microscope and the result was expressed in percentages. During the interim, the treated plants were kept in greenhouse compartments at 25C.

The compounds according to Example I were active in the above test against eggs, larvae and adults of Tretranychus urticae.

We claim:

1. A compoundpf the formula wherein R represents methyl or ethyl,

R represents n-propyl, isobutyl or sec. butyl,

R and R each represents hydrogen, chlorine, bromine, methyl or ethyl, R represents CH,CH=CHCI,

and X represents oxygen or sulphur.

2. A compound according to claim 1, wherein R, represents n-propyl or sec. butyl, and X represents oxygen.

3. A compound according to claim 2, wherein R represents ethyl, R and R each represents hydrogen, chlorine, bromine, or methyl, R is in ortho-position and X represents oxygen.

4. O-ethyl-S-n-propyl-O-[2-(3-chloroallyl)phenyl]- thiolphosphate, according to claim 3.

5. O-ethyl-S-n-propyl-O- 2-( 3-chloroallyl )-4- methylphenyl]-thiolphosphate, according to claim 3.

6. O-ethyl-S-n-propyl-O- 2-( 3 -chloroallyl )-4- bromophenyl]-thiolphosphate, according to claim 3.

7. O-ethyl-S-n-propyl-O-[ 2-( 3-chloroallyl )-4- chlorophenyl]-thiolphosphate,according to claim 3.

8. O-ethyl-S-n-propyl-O-[ 2-( 2-chloroallyl )phenyl thiolphosphate, according to claim 3.

9. O-ethyl-S-sec. butyl-O-[2-(3-chloroallyl)phenyl]- thiolphosphate, according to claim 3.

10. O-ethyl-S-sec. butyl-O-[2-(2- chloroallyl)phenyl1-thiolphosphate, according to claim 3. 

1. A COMPOUND OF THE FORMULA
 2. A compound according to claim 1, wherein R2 represents n-propyl or sec. butyl, and X represents oxygen.
 3. A compound according to claim 2, wherein R1 represents ethyl, R3 and R4 each represents hydrogen, chlorine, bromine, or methyl, R5 is in ortho-position and X represents oxygen.
 4. O-ethyl-S-n-propyl-O-(2-(3-chloroallyl)phenyl)-thiolphosphate, according to claim
 3. 5. O-ethyl-S-n-propyl-O-(2-(3-chloroallyl)-4-methylphenyl)-thiolphosphate, according to claim
 3. 6. O-ethyl-S-n-propyl-O-(2-(3-chloroallyl)-4-bromophenyl)-thiolphosphate, according to claim
 3. 7. O-ethyl-S-n-propyl-O-(2-(3-chloroallyl)-4-chlorophenyl)-thiolphosphate, according to claim
 3. 8. O-ethyl-S-n-propyl-O-(2-(2-chloroallyl)phenyl)-thiolphosphate, according to claim
 3. 9. O-ethyl-S-sec. butyl-O-(2-(3-chloroallyl)phenyl)-thiolphosphate, according to claim
 3. 10. O-ethyl-S-sec. butyl-O-(2-(2-chloroallyl)phenyl)-thiolphosphate, according to claim
 3. 